The present application relates to fabric care compositions which comprise one or more lysine and/or ornithine based polymers which provide enhanced fabric appearance benefits. The high molecular weight polyamino acids of the present invention which mitigate fabric damage and improve fabric appearance can be combined with other fabric softener actives to provide more complete mitigation of fabric damage.
The domestic treatment of fabric is a problem known in the art to the formulator of laundry compositions. Hence, It is well known that alternating cycles of using and laundering fabrics and textiles, such as articles of worn clothing and apparel, will inevitably adversely affect the appearance and integrity of the fabric and textile items so used and laundered. Fabrics and textiles simply wear out over time and with use. Laundering of fabrics and textiles is necessary to remove soils and stains which accumulate therein and thereon during ordinary use. However, the laundering operation itself, over many cycles, can accentuate and contribute to the deterioration of the integrity and the appearance of such fabrics and textiles.
Deterioration of fabric integrity and appearance can manifest itself in several ways. Short fibers are dislodged from woven and knit fabric/textile structures by the mechanical action of laundering. These dislodged fibers may form lint, fuzz or xe2x80x9cpillsxe2x80x9d which are visible on the surface of fabrics and diminish the appearance of newness of the fabric. Such a problem of fabric abrasion is even more acute after multiwash cycles.
There exists a long felt need for compositions which provide fabric with protection against damage done due to fabric abrasion. In addition, there is a long felt need to provide compositions which provide a remedy for fabric abrasion damage.
The present invention meets the aforementioned needs in that it has been surprisingly discovered that polymers comprising lysine and/or ornithine and other compatible amino acid and carboxylic acid residues are suitable for use in rinse-added fabric care compositions to provide provide fabric appearance benefits inter alia mitigation of fabric damage, prevention of fabric mechanical damage.
A first aspect of the present invention relates to rinse-added fabric enhancement or fabric care compositions comprising:
A) from about 0.1%, preferably from about 1%, more preferably from 2.5% to about 30%, preferably to about 20%, more preferably to about 10% by weight, of a polymeric material selected from the group consisting of:
a) homo-condensates of basic amino acids, said amino acids selected from the group consisting of lysine, ornithine, arginine, and tryptophan;
b) co-condensates of basic amino acids, said amino acids selected from the group consisting of lysine, ornithine, arginine, and tryptophan;
c) co-polymers produced from the reaction of one or more basic amino acids with one or more co-condensable compounds;
d) co-polymers produced from the reaction of one or more homo-condensates from (a) or co-condensates from (b) with one or more co-condensable compounds;
e) crosslinked basic amino acid-containing polymers, said crosslinked polymers comprising:
i) one or more basic amino acids;
ii) co-polymers of (i) and one or more co-condensable compounds;
iii) optionally co-polymers produced from the reaction of one or more homo-condensates from (a) or co-condensates from (b) with one or more co-condensable compounds; and
iv) one or more crosslinking unit;
wherein at least one crosslinking unit is derived from a crosslinker which comprises at least two functional groups;
f) co-condensates formed from the reaction of one or more compounds selected from the group consisting of:
i) basic amino acids;
ii) co-condensable compounds;
iii) crosslinking agents; and
g) mixtures thereof;
B) from about 1% to about 80% by weight, of a fabric softening active; and
C) the balance carriers and adjunct ingredients.
A second aspect of the present invention relates to fabric care compositions comprising:
A) from about 0.1%, preferably from about 1%, more preferably from 2.5% to about 30%, preferably to about 20%, more preferably to about 10% by weight, of a polymeric material selected from the group consisting of:
a) homo-condensates of basic amino acid, said amino acids selected from the group consisting of lysine, ornithine, arginine, and tryptophan;
b) co-condensates of basic amino acids, said amino acids selected from the group consisting of lysine, ornithine, arginine, and tryptophan;
c) co-polymers produced from the reaction of one or more basic amino acids with one or more co-condensable compounds.
d) co-polymers produced from the reaction of one or more homo-condensates from (a) or co-condensates from (b) with one or more co-condensable compounds;
e) crosslinked basic amino acid-containing polymers, said crosslinked polymers comprising:
i) one or more basic amino acids;
ii) co-polymers of (i) and one or more co-condensable compounds;
iii) optionally co-polymers produced from the reaction of one or more homo-condensates from (a) or co-condensates from (b) with one or more co-condensable compounds; and
iv) one or more crosslinking unit;
wherein at least one crosslinking unit is derived from a crosslinker which comprises at least two functional groups;
f) co-condensates formed from the reaction of one or more compounds selected from the group consisting of:
i) basic amino acids;
ii) co-condensable compounds;
iii) crosslinking agents:
g) optionally said homo-condensates from (a), co-condensates from (b), co-polymers from (c) and (d), crosslinked polymers from (e), and co-condensates from (f), are alkoxylated with from an average of 0.1 to about 30 alkyleneoxy units; and
h) mixtures thereof;
B) optionally from about 0.01% by weight, of a fabric anti-abrasion polymer comprising:
i) at least one monomeric unit comprising an amide moiety;
ii) at least one monomeric unit comprising an N-oxide moiety;
iii) and mixtures thereof;
C) optionally from about 1%, preferably from about 10%, more preferably from about 20% to about 80%, preferably to about 60%, more preferably to about 45% by weight, of a fabric softening active;
D) optionally less than about 15% by weight, of a principal solvent, preferably said principal solvent has a ClogP of from about 0.15 to about 1;
E) optionally from about 0.001% to about 90% by weight, of one or more dye fixing agents;
F) optionally from about 0.01% to about 50% by weight, of one or more cellulose reactive dye fixing agents;
G) optionally from about 0.01% to about 15% by weight, of a chlorine scavenger;
H) optionally about 0.005% to about 1% by weight, of one or more crystal growth inhibitors;
I) optionally from about 1% to about 12% by weight, of one or more liquid carriers;
J) optionally from about 0.001% to about 1% by weight, of an enzyme;
K) optionally from about 0.01% to about 8% by weight, of a polyolefin emulsion or suspension;
L) optionally from about 0.01% to about 0.2% by weight, of a stabilizer;
M) from about 0.01% by weight, of one or more linear or cyclic polyamines which provide bleach protection; and
N) the balance carrier and adjunct ingredients.
Another aspect of the present invention relates to rinse-added fabric enhancement or fabric care compositions comprising:
A) from about 0.1%, preferably from about 1%, more preferably from 2.5% to about 30%, preferably to about 20%, more preferably to about 10% by weight, of a polymeric material selected from the group consisting of:
a) homo-condensates of basic amino acid, said amino acids selected from the group consisting of lysine, ornithine, arginine, and tryptophan;
b) co-condensates of basic amino acids, said amino acids selected from the group consisting of lysine, ornithine, arginine, and tryptophan;
c) co-polymers produced from the reaction of one or more basic amino acids with one or more co-condensable compounds;
d) co-polymers produced from the reaction of one or more homo-condensates from (a) or co-condensates from (b) with one or more co-condensable compounds;
e) crosslinked basic amino acid-containing polymers, said crosslinked polymers comprising:
i) one or more basic amino acids;
ii) co-polymers of (i) and one or more co-condensable compounds:
iii) optionally co-polymers produced from the reaction of one or more homo-condensates from (a) or co-condensates from (b) with one or more co-condensable compounds; and
iv) one or more crosslinking unit;
wherein at least one crosslinking unit is derived from a crosslinker which comprises at least two functional groups;
f) co-condensates formed from the reaction of one or more compounds selected from the group consisting of:
i) basic amino acids;
ii) co-condensable compounds;
iii) crosslinking agents;
g) optionally said homo-condensates from (a), co-condensates from (b), co-polymers from (c) and (d), crosslinked polymers from (e), and co-condensates from (f), are alkoxylated with from an average of 0.1 to about 30 alkyleneoxy units; and
h) mixtures thereof;
wherein said polymers from (a), (b), (c), (d), (e), (f), or (g) have one or more backbone hydrogen atoms substituted with an alkyleneoxy unit having the formula xe2x80x94(RO)xH wherein R is C2-C30 alkylene and x has an average value of from 0.1 to about 100;
B) from about 1% to about 80% by weight, of a fabric softening active; and
C) the balance carriers and adjunct ingredients.
A further aspect of the present invention provides a method for enhancing the color fidelity of fabric while reducing the damage to fabric due to the interaction of laundry adjunct ingredients and damage due to mechanical wear. This method comprise the step of contacting an article of fabric with the compositions of the present invention in an aqueous solution.
The present invention further provides laundry pre-soak compositions which are used to pre-treat fabric which have not been previously treated with a composition of the present invention. The disclosed pre-treatment compositions provide fabric and fabric color protection through the wash to the treated articles.
These and other objects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (xc2x0 C.) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.
The present invention relates to fabric enhancement compositions which comprise from about 0.1%, preferably from about 1%, more preferably from 2.5% to about 30%, preferably to about 20%, more preferably to about 10% by weight, of one or more polymeric materials comprising lysine, ornithine, arginine, tryptophan, and mixtures thereof.
The basic amino acid-containing polymers of the present invention are selected from the group consisting of:
a) homo-condensates of basic amino acid, said amino acids selected from the group consisting of lysine, ornithine, arginine, and tryptophan;
b) co-condensates of basic amino acids, said amino acids selected from the group consisting of lysine, ornithine, arginine, and tryptophan;
c) co-condensate co-polymers produced from the reaction of one or more homo-condensates from (a) or co-condensates from (b) with one or more co-condensable compounds;
d) crosslinked basic amino acid-containing polymers, said crosslinked polymers comprising:
i) homo-condensates;
ii) optionally co-condensates;
iii) optionally co-polymers produced from the reaction of one or more basic amino acids with one or more co-condensable compounds;
iv) optionally co-polymers produced from the reaction of one or more homo-condensates from (i) or co-condensates from (ii) with one or more co-condensable compounds;
said compound or mixtures thereof further reacted with:
v) at least one crosslinker which comprises at least two functional groups as defined herein below;
e) co-condensates formed from the reaction of one or more compounds selected from the group consisting of:
i) basic amino acids;
ii) co-condensable compounds;
iii) crosslinking agents:
f) mixtures thereof; and
g) polymers (a), (b), (c), (d) or (e) which have one or more backbone hydrogen atoms substituted with an alkyleneoxy unit having the formula xe2x80x94(RO)xH wherein R is C2-C30 alkylene and x has an average value of from 0.1 to about 100, said alkyleneoxy unit substitution taking place during any step of the process for producing said alkyleneoxy substituted polymers.
For the purposes of the present invention the term xe2x80x9ccondensatesxe2x80x9d is used to refer to the polymers of groups (i), (ii), and (iii) separately or collectively. The following is a description of the polyamines suitable for use in the fabric enhancement compositions of the present invention.
Homo-condensates (a)
One aspect of the present invention relates to fabric enhancement compositions which comprise homo-condensates of xe2x80x9cbasic amino acidsxe2x80x9d, said basic amino acids are selected from the group consisting of lysine, ornithine, arginine, tryptophan, and mixtures thereof. Homo-condensates, which are polyamines of type (a), for the purposes of the present invention comprise one amino acid, for example, all lysine amino acids. Typically the homo-condensates are linked via the xcfx89-amino unit, however, linkage via the xcex1-amino unit is also an embodiment of the present invention as well as homo-condensates which are mixtures of both xcex1 and xcfx89 linkages.
Co-condensates (b)
Another aspect of the present invention relates to co-condensates which are a mixture of two or more basic amino acids, for example, a mixture of lysine and ornithine amino acids. Typically the homo-condensates are linked via the xcfx89-amino unit, however, linkage via the xcex1-amino unit is also an embodiment of the present invention as well as co-condensates which arc mixtures of both xcex1 and xcfx89 linkages. Typically the co-condensates are linked via the xcfx89-amino unit, however, linkage via the xcex1-amino unit is also an embodiment of the present invention as well as homo-condensates which are mixtures of both xcex1 and xcfx89 linkages.
In order to produce homo-condensates or co-condensates, basic amino acids are preferably condensed thermally. Other methods for the production of basic amino acid-containing polymers are based on chemical methods (e.g. via N-carboxy anhydrides of the basic amino acids) or on microorganisms. The basic amino acids, as defined herein above, are lysine, arginine, ornithine, tryptophan, and mixtures thereof. These compounds may be used in the form of their hydrates, ester of lower alcohols, or salts, for instance their sulfates, hydrochlorides or acetates. The esters of the basic amino acids are preferably derived from monovalent C1-C4 alcohols inter alia methanol, ethanol. When hydrochlorides are use, approximately equivalent quantities of a base should be added to the reaction mixture for neutralization of hydrogen chloride. Sodium hydroxide and potassium hydroxide are the preferred bases. If a monohydrochloride of a basic amino acid is used, one equivalent of a base is necessary whereas in case of dihydrochorides two equivalents are required. Lysine hydrate and aqueous solutions of lysine are preferably used as basic amino acid. Lysine can also be used in form of its cyclic lactam, i.e., xcex1-amine-xcex5-caprolactam.
For the purposes of the present invention the term xe2x80x9cweight average molecular weightxe2x80x9d, Mw, is defined herein as xe2x80x9cthe average molecular weight of a polymer admixturexe2x80x9d. Those skilled in the art will recognize that a homo-condensate with a Mw equal to 1000 daltons will comprise some amount of homo-condensates having a molecular weight less than 1000 daltons and some having a molecular weight greater than 1000 daltons.
The homo-condensates of the present invention have a Mw of from about 300 daltons to about 1,000,000 (million) daltons, preferably to about 20,000 daltons, more preferably to about 2,000 daltons.
Basic Amino Acid/Co-Condensable Compound Co-polymers (c)
A further aspect of the present invention relates to fabric enhancement compositions which comprise co-polymers which are the reaction product of one or more basic amino acids and one or more xe2x80x9cco-condensable compoundsxe2x80x9d. In their basic form these compounds are co-polymers produced from the reaction of one or more basic amino acids with one or more of the co-condensable compounds described herein below. xe2x80x9cCo-condensable compoundsxe2x80x9d are defined herein as xe2x80x9ccompounds which are capable of reacting with basic amino acids or other co-condensates to form polymeric materials having desirable propertiesxe2x80x9d. For the purposes of the present invention the term xe2x80x9cbasic amino acid/co-condensable compound co-polymersxe2x80x9d are defined herein as xe2x80x9cthe reaction product of one or more a basic amino acids prior to polymerization and one or more of the co-condensable compounds further described hereinxe2x80x9d.
For the purposes of the present invention the term xe2x80x9cethylenically unsaturatedxe2x80x9d is defined herein as xe2x80x9ca compound, aliphatic or otherwise, which comprises one double bond, for example, an olefin moietyxe2x80x9d. A preferred example of a single xe2x80x9cethylenically unsaturatedxe2x80x9d compound suitable for use in forming the condensable compounds and crosslinked compounds of the present invention is acrylic acid and derivatives therefrom, inter alia, methyl acrylate, acrylamide.
Non-limiting examples of compounds which are co-condensable with basic amino acids include:
i) compounds having at least one carboxyl group;
ii) carboxylic acid anhydrides;
iii) diketenes;
iv) amines;
v) lactams;
vi) alcohols;
vii) alkoxylated alcohols; and
viii) alkoxylated amines.
Carboxyl Group-containing Compounds (i)
Suitable carboxyl group-containing compounds include saturated mono basic carboxylic acids (alkyl carboxylic acids); unsaturated monobasic carboxylic acids (alkenyl carboxylic acids); poly basic carboxylic acids (di-carboxylic acids); mono hydroxycarboxylic acids; mono basic polyhydroxy carboxylic acids; non-proteinogenic amino acids, inter alia amino butyric acid, and mixtures thereof.
Non-limiting examples of saturated mono basic carboxylic acids (alkyl carboxylic acids) include C1-C30 linear alkyl carboxylic acids, inter alia, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid (hexanoic acid), caprylic acid (octanoic acid), nonanoic acid, capric acid (decanoic acid), undecanoic acid, lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidic acid (eicosanoic acid), behenic acid (docosanoic acid), C3-C30 branched alkyl carboxylic acids, inter alia, 2-ethyl hexanoic acid, as well as all other naturally occuring fatty acids and mixtures thereof.
Non-limiting examples of unsaturated mono basic carboxylic acids include C3-C30 alkenyl carboxylic acids, inter alia, acrylic acid, methacrylic acid, crotonic acid, sorbic acid, oleic acid, linolenic acid, and erucic acid.
Non-limiting examples of polybasic carboxylic acids include C2-C30 dicarboxylic acids, inter alia, oxalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, itaconic acid, adipic acid, aconitic acid, suberic acid, azeleic acid, pyridinedicarboxylic acid, furandicarboxylic acid, phthalic acid, terephthalic acid, diglycolic acid, glutaric acid, substituted C4-dicarboxylic acid, sulfosuccinic acid, C2-C26 alkylsuccinic acids, C2-C21 alkenylsuccinic acids, 1,2,3-propanetricarboxylic acids, 1,1,3,3-propanetetracarboxylic acids, 1,1,2,2-ethanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,3-propanetetracarboxylic acid, 1,3,3,5-pentanetetracarboxylic acid, 1,2,4-benzene-tricarboxylic acid, and 1,2,4,5-benzenetetracarboxylic acid.
Non-limiting examples of mono- and polyhydroxy saturated and unsaturated carboxylic acids include C3-C30 dicarboxylic acids, inter alia, malic acid, tartaric acid, citric acid, isocitric acid, tartaric acid, mucic acid, glyceric acid, bis(hydroxymethyl)propionic acid, gluconic acid, and dihydroxystearic acid.
Non-limiting examples of non-proteinogenic amino acids include anthranilic acid, N-methylamino substituted acids, inter alia, N-methylglycine and dimethylaminoacetic acid, ethanolaminoacetic acid, N-carboxymethylamino acids, nitrilotriacetic acid, ethylene-diamineacetic acid, ethylenediarinotetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylenediaminotriacetic acid, diaminosuccinic acid, C4-C26 aminoalkyl-carboxylic acids, inter alia, 4-aminobutyric acid, 6-aminocaproic acid, and 11-aminoundecanoic acid.
Non-limiting examples of carboxyl group-containing compounds which are not xe2x80x9cbasic amino acidsxe2x80x9d or other a-amino acids but which are suitable for condensation with the basic amino acids of the present invention include mono-saccharide carboxylic acids, inter alia, gluconic acid, glutaric acid, gluconolactone, and glucuronic acid.
Carboxylic Acid Anhydrides (ii)
Carboxylic anhydrides are also suitable as co-condensable compounds non-limiting Examples of which include succinic anhydride, mono and di-anhydride of butanetetracarboxylic acid, phthalic anhydride, acetylcitric anhydride, maleic anhydride, itaconic anhydride, and aconitic anhydride.
Diketenes (iii)
Diketenes which are suitable co-condensable compounds according to the present invention include C1-C30 substituted diketenes having the formula: 
wherein R1 and R2 are each independently hydrogen, C1-C30 saturated or ethylenically unsaturated alkyl. Non-limiting examples of diketenes include diketene, methyl diketene, hexyl diketene, cyclohexyl diketene, octyl diketene, decyl diketene, dodecyl diketene, palmityl diketene, stearyl diketene, oleyl diketene, eicosyl diketene, docosyl diketene, and behenyl diketene.
Amines (iv)
Non-limiting examples of amines which are suitable co-condensable compounds according to the present invention include C1-C30 aliphatic and cycloaliphatic amines, preferably methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, stearylamine, palmitylamine, 2-ethylhexylamine, isononylamine, hexamethyleneamine, dimethylamine, dicthylamine, dipropylaminc, dibutylamine, dihexylamine, ditridecylamine, N-methylbutylamine, N-ethylbutylamine, alicyclic amines, preferably cyclopentylamine, cyclohexylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, dicyclohexylamine. Also suitable for use as co-condensable compounds according to the present invention are diamines, triamines, and tetraamines, non-limiting examples of preferred polyamines include ethylenediamine, propylene-diamine, butylenediamine, neopentyldiamine, hexamethylenediamine, octamethylene-diamine, imidazole, 5-amino-1,3-trimethylcyclohexylmethylamine, diethylenetriamine, dipropylenetriamine, tripropyltetra-amine, 4,4xe2x80x2-methylenebiscyclohexylaminc, 4,4xe2x80x2-methyneibis(2-methylcyclohexylamine), 4,7-dioxa-decyl-1,10-diamine, 4,9-dioxadodecyl-1,12-diamine, 4,7,10-trioxatridecyl-1,13-diamine, 2-(ethylamino)ethylamine, 3-(methylamino)propylamine, 3-(cyclohexylamino)ethylamine, 3-(2-aminoethyl)amino-propylamine, 2-(diethylamino)ethylamine, 3-(dimethylamino)propylamine, dimethyldipropylene-triamine, 4-aminomethyloctne-1,8-diamine, 3-(diethylamino)-propylamine, N,N-diethyl-1,4-pentanedimane, diethylcnetriamine, dipropylenetriamine, bis(hexamethylene)triamine, aminoethyl-piperazine, aminopropylpiperazine, NN-bis(aminopropyl)methylamine, N,N-bis(aminopropyl)-ethylamine, N,N-bis(aminopropyl)-hexylamine, N,N-bis(aminopropyl)octylamine, N,N-dimethyldi-propylenetriamine, N,N-bis(3-dimethylaminopropyl)amine, N,Nxe2x80x2-1,2-ethanediylbis-(1,3-propane-diamine), N-(aminoethyl)piperazine, N-(2-inidazole)piperazine, N-ethylpiperazine, N-(hydroxyethyl)-piperazine, N-(aminopropyl)piperazine, N-(aminoethyl)morpholine, N-(aminopropyl)-morpholine, N-(aminoethyl)imidazole, N-(aminopropyl)imidazole, N-(aminoethyl)hexamethylenediamine, N-(aminopropyl)hexamethylenediamine, N-(aminoethyl)ethylene-diamine, N-(aminopropyl)ethylene-diamine, N-(aminoethyl)butylenediamine, N-(aminopropyl)butylenediamine, bis(aminoethyl)piperazine, bis(aminopropyl)piperazine, bis(aminoethyl)hexamethylenediamine, bis(aminopropyl)hexamethylene-diamine, bis(aminoethyl)ethylenediamine, bis(aminopropyl)ethylenediamine, bis(aminoethyl)-butylenediamine, and bis(aminopropyl)butylenediamine.
Included within the category of xe2x80x9caminesxe2x80x9d which are suitable for use as co-condensates are amino alcohols, non-limiting examples of which include 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 2-(2-aminoethoxy)ethanol, 2-[2-aminoethyl)amino]ethanol, 2-methylaminoethanol, 2-(ethylamino)ethanol, 2-butylaminoethanol, ethanolamine, 3-[(hydroxyethyl)-amino]-1-propanol, diisopropanolamine, bis(hydroxyethyl)aminoethylamine, bis(hydroxypropyl)amino-ethylamine, bis(hydroxyethyl)amino-propylamine, and bis(hydroxypropyl)aminopropylamine.
Also included in the category of xe2x80x9caminesxe2x80x9d which are suitable for use as co-condensates are amino-saccharides, non-limiting examples of which include chitosan, chitosamine, and compounds which are obtained from reducing sugars (carbohydrates) by reductive amination, inter alia, aminosorbitol and glucoseamine.
Further included in the category of xe2x80x9caminesxe2x80x9d which are suitable for use as co-condensates are other amino-group containing compounds, inter alia, melamine, urea, guanidine, polyguanides, piperidine, morpholine, 2,6-dimetylmorpholin, tryptamine.
Lactams (v)
Non-limiting examples of lactams which are suitable co-condensable compounds according to the present invention are those which comprise from 5 to 13 carbon atoms in the lactam ring, non-limiting examples of which include butyrolactam, caprolactam, valerolactam, and laurolactam.
Alcohols (vi)
Non-limiting examples of C1-C22 primary, secondary, and tertiary alcohols which are suitable co-condensable compounds according to the present invention include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol, hexanol, 2-ethylhexanol, cyclohexanol, octanol, decanol, dodecanol, palmityl alcohol, stearyl alcohol, and behenyl alcohol. Further suitable alcohols include polyols, for example, ethylene glycol, propylene glycol, glycerol, polyglycerols having for 2 to 8 glycerol units, erythritol, pentacrythritol, and sorbitol.
Other alcohols which are suitable co-condensable compounds according to the present invention include carbohydrates, inter alia, glucose, sucrose, dextrins, starch and degraded starch and maltose.
Alkoxylated Alcohols (vii)
Non-limiting examples of alkoxylated alcohols which are suitable co-condensable compounds according to the present invention are the addition products of from 1 to 200 moles of C2-C4 alkylene oxides with one mole of the hereinbefore described alcohols (vi). Suitable alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide, preferably ethylene oxide and propylene oxide, more preferably ethylene oxide. A further preferred embodiment comprises mixtures of propylene oxide and ethylene oxide wherein said oxides are added in any order. Also suitable for use in the present application are addition products of from 3 to 30 moles of ethylene oxide with 1 mole of C13-C15 oxo process alcohols or with fatty alcohols. The alcohols may also be alcohols which comprise double bonds inter alia oleyl alcohol.
Alkoxylated Amines (viii)
Non-limiting examples of alkoxylated amines which are suitable co-condensable compounds according to the present invention are the addition products of from 5 to 30 moles of ethylene oxide with 1 mole of an aliphatic amine, inter alia, stearylamine, oleylamine or palmitylamine.
Homo-condensate/Co-condensate Condensable Compound Co-polymers (d)
A further aspect of the present invention relates to fabric enhancement compositions which comprise homo-condensates or co-condensates of basic amino acids and xe2x80x9cco-condensable compoundsxe2x80x9d. In their basic form these compounds are co-polymers produced from the reaction of one or more homo-condensates from (i) or co-condensates from (ii) w with one or more co-condensable compounds. xe2x80x9cCondensable compoundsxe2x80x9d are defined herein as compounds which are capable of reacting with pre-formed homo-condensates or co-condensates to form polymeric materials having desirable properties. For the purposes of the present invention the term xe2x80x9chomo-condensate/co-condensate condensable compound co-polymerxe2x80x9d is defined herein as xe2x80x9cthe reaction product of a homo-condensate or co-condensate and one or more co-condensable compound as described hereinxe2x80x9d.
Crosslinked Basic Amino Acid-containing Polymers (e)
A further aspect of the present invention relates to crosslinked basic amino acid-containing polymers wherein homo-condensates and/or co-condensates are further crosslinked with a suitable crosslinker described herein below. In general, the crosslinked polymers of the present invention comprise:
i) homo-condensates;
ii) optionally co-condensates;
iii) optionally co-polymers produced from the reaction of one or more basic amino acids with one or more co-condensable compounds;
iv) optionally co-polymers produced from the reaction of one or more homo-condensates from (i) or co-condensates from (ii) with one or more co-condensable compounds;
which are further reacted together to form a basic amino acid containing polymer, said polymer with:
v) at least one crosslinker which comprises at least two functional groups as defined herein below.
For the purposes of the present invention the term xe2x80x9cfunctional groupxe2x80x9d is defined herein as xe2x80x9ca moiety which serves to form a bond between the crosslinking unit and the basic amino acid-containing polymer units which are being crosslinked.xe2x80x9d Non-limiting examples of functional groups are halogen units, which are for example, displaced by the amino units of the polyamine backbone, during the process of forming the crosslinks. An example of a preferred functional group is the ethylene or olefin unit referred to throughout the present specification as an xe2x80x9cethylenically unsaturatedxe2x80x9d unit. This functional group serves during crosslinking reactions as a Michael addition acceptor thereby forming a bond between the amino unit of the condensates and the crosslinking unit.
The crosslinked polyamines of the present invention can be formed by the reaction of the selected polyamine with a suitable crosslinker non-limiting examples of which include the xcex1-, xcfx89-, or vicinal dichloroalkanes 1,2-dichloroethane, 1,2-dichlorpropane, 1,3-dichloropropane, 1,4-dichlorobutane, and 1,6-dichlorohexane. Another example of a suitable crosslinker, but wherein the two functional groups are different, are the glycidyl halides non-limiting examples of which include epichlorohydrin, bis-chlorohydrins ethers of polyols, polychlorohydrin ethers of polyols, bis-chlorohydrin ethers of polyalkylene glycols, chloroformic acid esters. Another suitable crosslinking agent is phosgene.
Examples of preferred crosslinking units according to the present invention include epichlorohydrin, bis-chlorohydrin ethers of ethylene glycol, polyethylene glycol having 2 to 100, preferably 2 to 40 ethylene glycol units, propylene glycols, polypropylene glycols, copolymers of ethylene oxide and propylene oxide, glycerol, diglycerol, polyglycerol having up to 8 glycerol units, pentaerythritol and sorbitol.
The preferred crosslinkers of the present invention are halogen-free crosslinkers. Non-limiting examples of preferred bifunctional crosslinkers of the present invention are selected from the group consisting of:
i) ethylene carbonate, propylene carbonate, urea, or mixtures thereof;
ii) monoethylenically unsaturated carboxylic acids and their esters, amides, and anhydrides; dibasic saturated carboxylic acids, polycarboxylic acids and the esters, amides, and anhydrides derived therefrom;
iii) reaction products of:
a) polyether diamines, alkylene diamines, polyalkylene polyamines, alkylene glycols or polyalkylene glycols, and mixtures thereof; and
b) monoethylenically unsaturated carboxylic acids, esters, amides, or anhydrides wherein the reaction products comprise at least two units selected from the group consisting of ethylenically unsaturated double bonds, carboxamide, carboxyl, ester groups, and mixtures thereof;
iv) reaction products of dicarboxylic acid esters with ethyleneimine, wherein said products comprise at least two aziridino units;
v) di-epoxies, polyepoxides, xcex1,xcfx89-diisocyanates hexamethylene diisocyanate, inter alia, and polyisocyanates;
vi) and mixtures thereof.
Crosslinker Group (i)
The crosslinkers of group (i) comprise cyclic carbonates non-limiting examples of which include ethylene carbonate and propylene carbonate, as well as other carbonyl comprising crosslinking units, urea, inter alia. A preferred crosslinker from (i) is propylene carbonate.
Crosslinker Group (ii)
Non-limiting examples of suitable crosslinkers from (ii) include monoethylenically unsaturated monocarboxylic acids, inter alia, acrylic acid, methacrylic acid, crotonic acid, an in addition the amides, esters and anhydrides derived therefrom. The esters can be derived from alcohols having from 1 to 22, preferably up to 18 carbon atoms, While the amides are preferably unsubstituted, they can, however, comprise a C1-C22 alkyl radical as the nitrogen substituent.
Halogen free crosslinkers from (ii) also include dibasic saturated carboxylic acids, their salts, diesters, and diamides derived therefrom having the formula: 
wherein X is xe2x80x94OH, xe2x80x94OR, xe2x80x94N(R1)2, and mixtures thereof; R is C1-C22 alkyl, and mixtures thereof; R1 is hydrogen, C1-C22 alkyl, and mixtures thereof; the index n if from 0 to 22. In addition, monoethylenically unsaturated dicarboxylic acids, non-limiting examples of which include maleic acid and itaconic acid, are suitable for use in forming the group (ii) crosslinkers.
Dicarboxylic acids which are preferred as crosslinkers are derived from C1-C4 alcohols, inter alia, methyl esters, non-limiting example of which include dimethyl oxalate, diethyl oxalate, diisopropyl oxalate, dimethyl succinate, diethyl succinate, diisopropyl succinate, di-n-propyl succinate, di-isobutyl succinate, dimethyl adipate, diethyl adipate, and di-isopropyl adipate, dimethyl maleate, diethyl maleate, di-isopropyl maleate, dimethyl itaconate, di-isopropyl itaconate, dimethyl tartrate, and diethyl tartrate. In the case of carboxylic acids having more than one optical isomer; inter alia, tanaric acid, all optical forms and the racemic mixture are equally suitable.
Non-limiting examples of suitable dicarboxylic acid anhydrides include maleic anhydride, itaconic anhydride, and succinic anhydride. Aziridines are crosslinked with the herein above described halogen-free crosslinkers with the formation of amide groups or, in the case of amides such as adipic acid diamide, by means of transamidation. Maleic esters, and monoethylenically unsaturated dicarboxylic acids, and also their anhydrides, can effect crosslinking both by forming carboxamide groups and also by adding xe2x80x94NH groups by means of a Michael addition.
Also suitable for use as group (ii) crosslinkers are tricarboxylic and tetracarboxylic acids non-limiting examples of which include citric acid, propanetricarboxylic acid, ethylenediaminetetraacetic acid and butanetetracarboxylic acid, as well as, their salts, esters, amides, and anhydrides.
Polycarboxylic acids which can be obtained by polymerizing mono-ethylenically unsaturated carboxylic acids or anhydrides are also suitable group (ii) crosslinkers. Non-limiting examples of suitable mono-ethylenically unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and mixtures thereof. Thus, for example, polyacrylic acids, copolymers of acrylic acid and methacrylic acid or copolymers of acrylic acid and maleic acid are suitable for use as crosslinkers.
Further suitable crosslinkers from group (ii) are prepared, for example, by polymerizing anhydrides, such as maleic anhydride, in an inert solvent, such as toluene, xylene, ethylbenzene, isopropyl benzene, or mixtures thereof in the presence of free radical-forming initiators. Preference is given to using peroxy esters, such as tert-butyl per-2-ethylhexanoate, as initiators. Copolymers of maleic anhydride for example copolymers of acrylic acid and maleic anhydride or copolymers of maleic anhydride and a C2-C30 olefin, are also suitable in addition to the homopolymers.
Further preferred crosslinkers are copolymers of maleic anhydride and isobutene or copolymers of maleic anhydride and di-isobutene. The anhydride group-containing copolymers may, where appropriate, be modified by reacting them with C1-C20 alcohols or ammonia, amines, or mixtures thereof, and be employed in this form as crosslinkers.
The molar mass, Mw, of the homopolymers and copolymers which is subsequently crosslinked is preferably from about 500 daltons to about 10,000 daltons, preferably to about 5,000 daltons.
When the carboxylic acids of group (ii) are used as crosslinking agents, they may be used in the form of their alkali metal salts or ammonium salts, preferably the sodium salt. Optionally, the polycarboxylic acids can be partially neutralized, e.g., up to from 10 to 50 mol %, or else completely neutralized.
The preferred group (ii) crosslinkers are dimethyl tartrate, diethyl tartrate, dimethyl adipate, diethyl adipate, dimethyl maleate, diethyl maleate, maleic anhydride, maleic acid, acrylic acid, methyl acrylate, ethyl acrylate, acrylamide, methacrylamide, and mixtures thereof.
Crosslinker Group (iii)
Examples of halogen-free group (iii) crosslinkers are the reaction products of polyether diamines, alkylene diamines, polyalkylene polyamines, alkylene glycols, polyalkylene glycols, and mixtures thereof, together with:
a) monoethylenically unsaturated carboxylic acids;
b) esters of monoethylenically unsaturated carboxylic acids;
c) amides of monoethylenically unsaturated carboxylic acids;
d) anhydrides of monoethylenically unsaturated carboxylic acids; and
e) mixtures thereof.
The polyether diamines are prepared, for example, by reacting polyalkylene glycols with ammonia. The polyalkylene glycols can contain from 2 to 50, preferably to 40, alkylene oxide units. The polyalkylene glycols can, for example, be polyethylene glycols, polypropylene glycols or polybutylene glycols, or block copolymers of ethylene glycol and propylene glycol, block copolymers of ethylene glycol and butylene glycol or block copolymers of ethylene glycol, propylene glycol, and butylene glycol. Apart form the block copolymers, copolymers which are randomly assembled form ethylene oxide and propylene oxide and also, where appropriate, butylene oxide are also suitable for preparing the polyether diamines. In addition, polyether diamines are derived from polytetrahydro-furans which possess from 2 to 75 tetrahydrofuran units. The polytetrahydrofurans are likewise converted by reaction with ammonia into the corresponding xcex1- xcfx89- polyether diamines. Preference is given to using polyethylene glycols or block copolymers of ethylene glycol and propylene glycol for preparing the polyether diamines.
Non-limiting examples of suitable alkylene diamines include ethylenediamine, propylenediamine, 1,4-diaminobutane, and 1,6-diaminohexane. Non-limiting examples of suitable polyalkylene polyamines include diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetramine, aminopropylethylenediaamine, bis-aminopropylethylenediamine, and polyethyleneimines having Mw up to about 5000 daltons. The herein above described amines are reacted with mono-ethylenically unsaturated carboxylic acids, esters, amides or anhydrides of monoethylenically unsaturated carboxylic acids, such that the resulting products possess at least 2 ethylenically unsaturated double bonds, carboxamide, carboxyl, or ester group, as functional groups. Thus, for example, when the amines or glycols under consideration are reacted with maleic anhydride, compounds are obtained which can, for example, be characterized with the aid of the formula: 
wherein X, and Z are each independently oxygen, xe2x80x94NHxe2x80x94, and mixtures thereof, Y is oxygen, xe2x80x94NHxe2x80x94, xe2x80x94CH2xe2x80x94, and mixtures thereof, m and n are each independently from 0 to 4 and p and q are each independently form 0 to 45,000.
Polyether diamines, alkylene diamines and polyalkylene polyamines can also react with maleic anhydride, or the ethylenically unsaturated carboxylic acids or their derivatives, while adding onto the double bond by means of a Michael addition. Crosslinkers having the formula: 
wherein X, and Z are each independently oxygen, xe2x80x94NHxe2x80x94, and mixtures thereof; Y is oxygen, xe2x80x94NHxe2x80x94, xe2x80x94CH2xe2x80x94, and mixtures thereof; R1 is hydrogen, methyl, and mixtures thereof; R2 is hydrogen, xe2x80x94CO2R4, xe2x80x94CO2M, xe2x80x94CONH2, and mixtures thereof; R3 is xe2x80x94OR4, xe2x80x94NH2, xe2x80x94OH, xe2x80x94OM, and mixtures thereof; R4 is C1-C22 alkyl, M is hydrogen or a salt forming cation, preferably Na, K, Mg, Ca, and mixtures thereof; m and n are each independently from 0 to 4 and p and q are each independently form 0 to 45,000.
The herein above described crosslinkers, due to their terminal carboxyl or ester units, and with the formation of an amide function, a crosslinking with the amino groups of the polymers which are produced during the polymerization. This class of crosslinkers also includes the reaction products of monoethylenically unsaturated carboxylic esters with alkylene diamines and polyalkylene polyamines; for example the products which result from the addition of ethylenediamine, diethylenetriamine, having molar masses from 129 to 50,000 to acrylic esters or methacrylic esters, with at least 2 mole of the acrylic ester or methacrylic esters being employed.
An example of a crosslinking unit comprising a polyamine which is reacted with a compound having the formula: 
are compounds having the formula: 
wherein X is xe2x80x94NH2, xe2x80x94OH, xe2x80x94OR1, and mixtures thereof, R1 is C1-C22 alkyl.
Crosslinker Group (iv)
A preferred example of a crosslinker which is the reaction product of dicarboxylic acid esters with ethyleneimine, wherein said crosslinkers comprise at least two aziridino units has the formula: 
wherein n is from 0 to 22.
Crosslinker Group (v)
Crosslinker group (v) comprises di-epoxies, polyepoxides, xcex1,xcfx89-diisocyanates hexamethylene diisocyanate, inter alia, and polyisocyanates. Non-limiting examples of compounds which comprise the crosslinkers of group (v) include bis-glycidyl ethers of ethylene glycol, polyethylene glycol having 2 to 40 ethylene glycol units, propylene glycol, polypropylene glycol ethers, co-polymers of ethylene oxide and propylene oxide and diisocyanates, inter alia, hexamethylene diisocyanate.
Crosslinker Group (vi)
It is also preferred, according to the present invention to use a mixture of crosslinking units, non limiting examples of which include:
a) mixtures of di-glycidyl ethers of ethylene glycol and bis-chlorohydrin ethers of ethylene glycol;
b) mixtures of di-glycidyl ethers of polyethylene glycols having form 2 to 40 ethylene glycol units with bis-chlorohydrin ethers of polyethylene glycols having from 2 to 40 ethylene glycol units;
c) mixtures of hexamethylene di-isocyanate with propylene carbonate.
The following are non-limiting examples of basic-amino acid containing polymers according to the present invention.
Co-condensates of One or More Basic Amino Acids, Co-Condensable Compounds, or Crosslinking Units (f)
A further aspect of the present invention relates to fabric enhancement compositions which comprise co-condensates of one or more basic amino acids, homo-condensates or co-condensates of basic amino acids, xe2x80x9cco-condensable compoundsxe2x80x9d as defined herein above, and xe2x80x9ccrosslinking unitsxe2x80x9d as described herein above. In their basic form these compounds are co-polymers produced from the reaction of one or more basic amino acids, homo-condensates or co-condensates of basic amino) acids, xe2x80x9cco-condensable compoundsxe2x80x9d as defined herein above, and xe2x80x9ccrosslinking unitsxe2x80x9d taken in any order or in any relative amount. For example, the first step may comprise the reaction of one or more basic amino acids with a crosslinking unit which is subsequently followed by the addition of one or more co-condensable compounds. As described herein below, the resulting co-polymers may be optionally alkoxylated.
Alkoxylated Basic Amino Acid-containing Polymers
A preferred embodiment of the present invention comprises homo-condensates, co-condensates, co-polymers produced from the reaction of one or more homo-condensates from (i) or co-condensates from (ii) with one or more co-condensable compounds, and mixtures thereof which are further reacted with one or more alkylene oxides to form alkoxylated polyamines which are suitable for use in the fabric enhancement compositions of the present invention.
The condensed basic amino acid-containing compounds which can be further modified by alkoxylation comprise:
a) condensates of basic amino acids:
i) homo-condensates comprising a single basic amino acid;
ii) co-condensates comprising a mixture of two or more basic amino acids;
b) co-polymers produced from the reaction of one or more basic amino acids and one or more co-condensable compounds;
c) co-polymers produced from the reaction of one or more of the homo-condensates (i) or co-condensates (ii) with one or more co-condensable compounds;
d) crosslinked polymers as described herein; and
e) co-condensates formed from the reaction of one or more compounds from (a), (b), (c), or (d).
Non-limiting examples of preferred basic amino acid-containing polymers which are subsequently alkoxylated include polymers which are obtained by reaction of:
a) lysine; and
b) at least one compound selected from the group consisting of palmitic acid, stearic acid, lauric acid, octanoic acid, propionic acid, acetic acid, 2-ethylhexanoic acid, adipic acid, succinic acid, citric acid, and mixtures thereof.
The products which are formed from the reaction of the above components preferably comprise a molar ratio of lysine to compounds of group (b) of from 100:1 to 1:10. More preferably it is desirable that the pre-alkoxylated basic amino acid-containing polymer comprise a greater amount of lysine, or any other basic amino acid which comprises group (a), inter alia, ornithine, to have a ratio of the amino acid from (a) to be present in a ratio of at least 1.5: 1. Yet more preferably the elements which comprise (a) are present with respect to the elements which comprise (b) in a ratio greater than or equal to 2:1.
A further non-limiting example of preferred basic amino acid-containing polymers which are subsequently alkoxylated include polymers which are obtained by reaction of:
a) lysine; and
b) at least one compound selected from the group consisting of 1,6-hexandiamine. octylamine, aminocaproic acid, aminolauric acid, xe2x80x94-caprolactam, laurolactam, and C14-C22 alkyldiketenes.
The formulator may substitute for the basic amino acid, lysine, in (a) above, any of the other basic amino acids ornithine, arginine, tryptophan, or mixtures of any or all of the basic amino acids according to the present invention.
The above described preferred basic amino acid-containing polymers which are subsequently alkoxylated can be suitably obtained by any means chosen by the formulator, a non-limiting example of which includes carrying out the reaction in an organic solvent or in an aqueous medium. It is of advantage to conduct the condensation in water at a concentration of the compounds to be condensed of from 10 to 98% by weight, at a temperature of from 120xc2x0 C. to 300xc2x0 C. In a preferred embodiment of the process the condensation is carried out in water at a concentration of the compounds to be condensed of from 20 to 70% by weight, under pressure at a temperature of from 140xc2x0 C. to 250xc2x0 C. The condensation of these compounds can also be carried out in an organic solvent such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, glycol, polyethylene glycol, propylene glycol, polypropylene glycol, monovalent alcohols, addition products of ethylene oxide and/or propylene oxide to monovalent alcohols, to amines of to carboxylic acids. Some of these solvents may react with the basic amino acids.
Depending upon which elements are selected from groups (a) and (b) and the process chosen by the formulator, the amino groups of the starting material can be present as free amines or in form of their ammonium salts which can be obtained by partial or complete neutralization with a mineral acid, e.g., hydrochloric acid, phosphoric acid, or sulfuric acid, or with an organic acid such as methane sulfonic acid, acetic acid, formic acid, propionic acid, or citric acid.
The prefered basic amino acid-containing polymers of the present invention prior to alkoxylation have a Mw of from about 300 daltons to about 1,000,000 (million) daltons, preferably to about 20,000 daltons, more preferably to about 2,000 daltons.
The basic amino acid comprising polymers once formed, are suitably modified by alkoxylation such that they comprise alkyleneoxy units obtained by the reaction of said polymers with C2-C30 alkylene oxides, styrene oxide, and mixtures thereof The alkylene oxides are preferably selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. The xe2x80x9calkoxylatesxe2x80x9d defined herein as xe2x80x9cbasic amino acid-containing polymers wherein the hydrogen atoms of primary amino units, xe2x80x94NH2 units, and secondary amino units, xe2x80x94NH units, are replaced by alkyleneoxy units having the formula xe2x80x94(RO)xH wherein R is C2-C30 alkylene and x has an average value of from 0.1, preferably from 0.5 to 100, preferably to 30xe2x80x9d. These values of alkoxylation can be suitably obtained by reaction of the starting polyamine with from 0.1 moles, preferably 0.5 moles to 100, preferably to 30 moles of an alkylene oxide added, i.e., in condensed form. The most preferred altylene oxides are ethylene oxide, propylene oxide, and mixtures thereof. Most preferred are polymers which comprise from about 0.7 to about 2.5 alkyleneoxy units per replaced hydrogen atom and polymers which comprise from about 17 to about 25 alkyleneoxy units per replaced hydrogen atom.
In addition, crosslinked basic amino acid-containing polymers according to the present invention may be suitably alkoxylated, or alternatively, basic amino acid-containing polymers may be suitably alkoxylated then subsequently crosslinked according to the herein described procedures.